2,4,6-三硝基-2,4,6-三氮杂环己酮生成历程的~(15)N NMR研究

由DPT与脲或硝基脲在硝化剂中反应可以合成2,4,6-三硝基-2,4,6-三氮杂环己酮。本文用~(15)N示踪原子对DPT分子中不同位置的氮原子分别进行标记,用~(15)N NMR谱图来考察~(15)N标记的反应物和产物分子中标记原子的位置及丰度。结果表明,与脲或硝基脲缩合的DPT硝解碎片为非硝基取代的N,N-二羟甲基胺,硝基脲上硝基与硝化剂之间存在着交换反应。     

O(~1D)+Si(CH_3)_3Cl反应生成振动激发的OH(υ≤5)

实验光谱学和理论计算都发现,“重原子”能隔离分子中的某些振动能景,如SiH_4中Si—H振动泛频的“局域模”.Roger 等在研究F 原子与M(CH_2CH=CH_2)_4(M=Sn,Ge)的反应中,发现了Sn,Ge 对过剩能量转移到其它部分有强烈的阻碍作用(在中间态的寿命时间内).最近,在研究O(~1D)+M(CH_3)_4生成OH(v)反应中,观测到类似的现象.M=C 时,Lutz 用激光诱导荧光方法检测OH 的振动分布,振动是冷的,v=1与v=0的布居比为0.05,     

Kinetic study of the reaction of CH3O with Br and Br2

The title reactions have been studied at room temperature by applying the discharge flow method coupled with laser induced fluorescence detection of methoxy radicals and resonance fluorescence detection of bromine atoms. The following rate constants were determined: CH₃O + Br Õ products (1) k ₁ (298 K) = (3.4 ± 0.4 (1)) × 10¹³ cm³ mol^-1 s^-1, CH₃O + Br₂ Õ products (2) k ₂ (298 K) £ 5 × 10⁸ cm³ mol^-1 s^-1.     

金属配合物-寡聚核苷酸定位断裂剂研究进展

核酸切割试剂与寡聚核苷酸(ODN)偶联制得的人工核酸酶能在特定位点断裂DNA或RNA,为人工核酸酶的分子设计提供了一种新方法.本文综述了金属配合物-ODN识别切割试剂的偶联方式及其与靶分子的作用机制,并指出了今后的研究方向.     

Atom-probe field ion microscopy

The atom probe field ion microscope (AP-FIM) is a combination of a field ion microscope and a time-of-flight mass spectrometer with a single ion detection sensivity. With the field ion microscope topology of a surface, surface reactions and surface modifications can be studied in atomic detail. By time-of-flight measurements surface layers and interface layers can be chemically analyzed atom by atom and atomic layer by atomic layer. Compositional variations according to surface or interface segregation, precipitations, or surface changes in corrosion or in electrochemical layer formation etc. can be studied quantitatively on a subnanometer scale. Some of our studies on related problems will be decribed briefly.     

超球谐展开的收敛行为He原子的^3S态

利用相关函数－超球谐－广义Ｌａｇｕｅｒｒｅ函数方法，研究Ｈｅ原子＾３Ｓ态波函数向超球谐函数展开的收敛行为。截止于ｌ＝０，１，２的超球谐函数给出的本征能分别与组态相互作用的ｓ－，ｓｐ－，ｓｐｄ－极限能一致。仅用４４个超球谐函数，便得到了与精确的ＨｙｌｌｅｒａａｓＣＩ变分能量小数点后第５位的２＾３Ｓ，３＾３Ｓ的４＾３Ｓ态本征能吻合。     

金属Cu低指数表面熔化行为的分子动力学模

采用Mishin镶嵌原子势, 通过分子动力学方法模拟了金属Cu的低指数表面在不同温度的表面熔化行为, 分析了熔化过程中系统结构组态的变化以及固-液界面迁移情况. 金属Cu的(100)和(110)表面在低于熔点发生预熔化, 而(111)表面存在明显的过热现象. 准液体层的厚度随温度升高而增加, 热稳定性与表面的密排顺序一致, 按(111)、(100)、(110)顺序增大. 当温度高于热力学熔点时, 固液界面的移动速度与温度成正比, 外推得到热力学熔点约为1360～1380 K, 与实验结果1358 K吻合良好. 动力学系数定义为界面移动速度与过热程度的比值, 表现为明显的各向异性: k100=39 cm•s−1•K−1, k110=29 cm•s−1•K−1, k111=20 cm•s−1•K−1. k100与k110之间的比例符合collision-limited理论, (111)密排面有与其它低指数表面不同的熔化方式.     

Preparation of Nano-Sized γ-Al2O3 Supported Iron Catalyst for Fischer-Tropsch Synthesis by Solvated Metal Atom Impregnation Methods

Two types of small iron clusters supported on γ-Al2O3-RT(dehydroxylated at room temperature) and γ-Al2O3-800 (dehydroxylated at 800 ℃) were prepared by solvated metal atom impregnation (SMAI) techniques. The iron atom precursor complex, bis(toluene)iron(0) formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, M(o)ssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis(toluene)iron(0), and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced α-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.     

Synthesis and Characterization of Two Novel High Valent Dinuclear Complexes with a Triphenolate Ligand Bearing Functional Groups

Two novel high valent complexes [M2(III, III)L(p--OAc)2].PF6 (M=Mn, Fe; 9) were prepared, where L was the tri-anion of 2,6-bis{[(2-hydroxy-3-(morpholin-4-yl methyl)-5-tertbutyl benzyl)(pyridyl-2-methyl)amino]methyl}-4-methyl phenol which contained additional phenolic, tert-butyl and morpholin-4-yl methyl groups compared to its parent [Mn2(Ⅱ, Ⅱ)(bpmp)(μ-OAc)2]-ClO4 (10). These improvements decreased the difference between the new model and (Mn)4 cluster (OEC in nature).     

基于支持向量机的羰基化合物红外光谱研究

设计了一个4层分等级分类系统，通过支持向量机技术对羰基化合物的红外光谱成功地进行了信息分类和提取，并与人工神经网络进行比较，结果表明：支持向量机对羰基类化合物红外光谱分类效果优于人工神经网络；另外详细探讨了表征酰胺类化合物的特征光谱峰片段对识圳伯仲叔酰胺的影响，证明了酰胺的N-H伸缩振动峰对识别伯仲叔酰胺贡献最大，为构建红外光谱智能解析系统提供了定量依据。